Catalyst and process for thermo-neutral reforming of petroleum-based liquid hydrocarbons

Abstract

A process for producing a hydrogen-rich gas stream from a liquid hydrocarbon stream, the process comprising the steps of introducing the liquid hydrocarbon stream to a dual catalytic zone, the liquid hydrocarbon stream comprises liquid hydrocarbons selected from the group consisting of liquid petroleum gas (LPG), light naphtha, heavy naphtha, gasoline, kerosene, diesel, and combinations of the same, the dual catalytic zone comprises: a combustion zone comprising a seven component catalyst, and a steam reforming zone, the steam reforming zone comprising a steam reforming catalyst; introducing steam to the dual catalytic zone, introducing an oxygen-rich gas to the dual catalytic zone; contacting the liquid hydrocarbon stream, steam, and oxygen-rich gas with the seven component catalyst to produce a combustion zone fluid; and contacting the combustion zone fluid with the steam reforming catalyst to produce the hydrogen-rich gas stream, wherein the hydrogen-rich gas stream comprises hydrogen.

That which is claimed is: 
     
       1. A process for producing a hydrogen-rich gas stream from a vaporized liquid hydrocarbon stream, the process comprising the steps of:
 introducing steam to a mixer, wherein the steam is a temperature between 200° C. and 400° C. and atmospheric pressure; 
 introducing an oxygen-rich gas to the mixer, wherein the oxygen-rich gas is selected from the group consisting of air, oxygen, oxygen enriched air, and combinations of the same 
 introducing a vaporized liquid hydrocarbon stream to the mixer, wherein the vaporized liquid hydrocarbon stream comprises liquid hydrocarbons selected from the group consisting of liquid petroleum gas (LPG), light naphtha, heavy naphtha, gasoline, kerosene, diesel, and combinations of the same; 
 mixing the steam, oxygen-rich gas, and vaporized liquid hydrocarbon stream to produce a mixed feed; 
 introducing the mixed feed to a dual catalytic zone, wherein the dual catalytic zone comprises: 
 a combustion zone comprising a seven component catalyst, the seven component catalyst consisting of: 
 nickel in an amount between 0.5 wt % and 15 wt % by weight of the catalyst, 
 rhodium in an amount between 0.1 wt % and 2 wt % by weight of the catalyst, 
 rhenium in an amount between 0.1 wt % and 2 wt % by weight of the catalyst, 
 platinum in an amount between 0.1 wt % and 2 wt % by weight of the catalyst, 
 cerium oxide in an amount between 0.5 wt % and 10 wt % by weight of the catalyst, 
 lanthanum oxide in an amount between 0.5 wt % and 5 wt % by weight of the catalyst, 
 zirconium oxide in an amount between 0.5 wt % and 3 wt % by weight of the catalyst, 
 a refractory support in an amount between 61 wt % and 97.7 wt %, and 
 a steam reforming zone downstream of the combustion zone, the steam reforming zone comprising a steam reforming catalyst, the steam reforming catalyst consisting of: 
 nickel in an amount between 0.5 wt % and 15 wt % by weight of the catalyst, 
 lanthanum oxide in an amount between 0.5 wt % and 5 wt % by weight of the catalyst, 
 cerium oxide in an amount between 0.5 wt % and 10 wt % by weight of the catalyst, and 
 an aluminate support in an amount between 70 wt % and 98.5 wt %; 
 contacting the mixed feed comprising the vaporized liquid hydrocarbon stream, steam, and oxygen-rich gas with the seven component catalyst to produce a combustion zone fluid; and 
 contacting the combustion zone fluid with the steam reforming catalyst to produce the hydrogen-rich gas stream, wherein the hydrogen-rich gas stream comprises hydrogen. 
 
     
     
       2. The process of  claim 1 , wherein a temperature of the combustion zone of the dual catalytic zone is in the range between 700° C. and 850° C., wherein a temperature of the steam reforming zone is in the range between 700° C. and 850° C. 
     
     
       3. The process of  claim 1 , wherein a pressure of the combustion zone of the dual catalytic zone is atmospheric pressure, and wherein a pressure of the steam reforming zone is atmospheric pressure. 
     
     
       4. The process of  claim 1 , further comprising the step of vaporizing a liquid hydrocarbon stream at a temperature between 150° C. and 250° C. and atmospheric pressure to produce the vaporized liquid hydrocarbon stream. 
     
     
       5. The process of  claim 1 , wherein the gas hour space velocity of the dual catalytic zone is less than 45,000 hr-1. 
     
     
       6. The process of  claim 1 , wherein a hydrogen concentration in the hydrogen-rich gas stream is greater than 60 percent volume in volume. 
     
     
       7. The process of  claim 1 , wherein the hydrogen-rich gas stream comprises additional product gases, wherein the additional product gases are selected from the group consisting of carbon monoxide, carbon dioxide, methane, nitrogen, and combinations of the same. 
     
     
       8. The process of  claim 1 , wherein the process is a continuous process. 
     
     
       9. The process of  claim 1 , wherein the hydrogen-rich gas stream is a fuel for a transportation vehicle. 
     
     
       10. The process of  claim 1 , wherein the steam reforming catalyst further comprises platinum present in an amount between 0.1 wt % and 2 wt % by weight of the catalyst and wherein the aluminate support is present in an amount between 68 wt % and 98.4 wt % by weight of the catalyst.